An Organic Origin for the Carbonate Concretions of the Ohio Shale -, I • llo I' ' l· • ' I I ~ ~ '-, ' ( • II 'I ' I - I I .. ... !. ·: 1 • I .;. ' ., " ' ~' . ' • •"' •, . • ... "': _.'I Instructions on ordering publications of the U.S. Geological Survey, along with prices of the last offerings, are given in the cur­ rent-year issues of the monthly catalog "New Publications of the U.S. Geological Survey." Prices of available U.S. Geological Sur­ vey publications released prior to the current year are listed in the most recent annual "Price and Availability List" Publications that are listed in various U.S. Geological Survey catalogs (see back inside cover) but not listed in the most recent annual "Price and Availability List'' are no longer available. 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Alaska Distribution Sedion, U.S. Geological Survey, • DENVER, Colorado--Map Distribution, lUdg. 810, Federal •• New Federal Building - Box 11 I Center 101 Twelfth Ave., Fairbanks, AK 99701 • FAIRBANKS, Alaska--New Federal Bldg., 101 Twelfth Ave. I I .- ... 1: - ,•_ ... • .. I I l' t I • 'I An Organic Origin for the Carbonate Concretions of the Ohio Shale By R.E. CRISS, G.A. COOKE, and S.D. DAY U.S. GEOLOGICAL SURVEY BULLETIN 1836 DEPARTMENT OF THE INTERIOR DONALD PAUL HODEL, Secretary U.S. GEOLOGICAL SURVEY Dallas L. Peck, Director UNITED STATES GOVERNMENT PRINTING OFFICE: 1988 For sale by the Books and Open-File Reports Section, U.S. Geological Survey Federal Center, Box 25425, Denver, CO 80225 Library of Congress Cataloging In Publication Data Criss, R.E. An organic origin for the carbonate concretions of the Ohio Shale (U.S. Geological Survey bulletin ; 1836) Bibliography: p. Supt. of Docs. no.: I 19.3:1836 1. Concretions-Ohio River Valley. 2. Rocks, Carbonate-Ohio River Valley. 3. Organic geochemistry-Ohio River Valley. 4. Ohio Shale. 5. Geology, Stratigraphic-Devonian. I. Cooke, G.A. II. Day, S.D. Ill. Title. IV. Series. QE75.89 no. 1836 557.3 s[552'.5] 87--600470 [QE471.15.C58] CONTENTS Abstract 1 Introduction 1 Acknowledgments 2 Methods 3 Field and petrographic relations 3 Lithology and petrology 3 Time of growth of the concretions 6 Stratigraphic zonation of the carbonate concretions 9 Isotopic and chemical relations 9 Chemical composition 9 Carbon and oxygen isotope data 12 Interpretation of the o13 C values 13 Interpretation of the o18 0 values 14 Discussion and conclusions 17 References 18 FIGURES 1. Map showing outcrop belt of Devonian Shales in Ohio 2 2. Photographs of typical concretions from the Huron Member of the Ohio Shale near Worthington, Ohio 4 3. Schematic diagram showing mineralogical zonation in the concretions from the Huron Member of the Ohio Shale 6 4. Gray shale dike crosscutting the Huron Member of the Ohio Shale along the Huron River near Milan, Ohio 7 5. Concretions incorporated in clastic dike and sill complex, along the Huron River near Milan, Ohio 8 6. Graphs showing radial distribution of chemical contents and o180 and o13C values in concretions from Worthington, Ohio 10 7. Graph of o180 vs. o13C values of carbonate concretions from the Huron Member of the Ohio Shale 13 8. Photographs of concretions with fossil fish from several localities 15 TABLES 1. X-ray spectrochemical data for concretions from the Huron Member of the Ohio Shale 11 2. Isotopic composition of concretions from the Huron Member of the Ohio Shale, Worthington, Ohio 12 3. o180 determinations of coexisting vug minerals in concretions of the Huron Member 13 4. Concretions from other localities-This study and others 14 Contents Ill An Organic Origin for the Carbonate Concretions of the Ohio Shale By R.E. Criss, 1 G.A. Cooke,2 and S.D. Day3 ABSTRACT hydrostatically supported the large, rapidly grown concre­ tions, which now have pee3 g/cc. Furthermore, as is typical of Pyrite-rimmed carbonate concretions of the low­ carbonate concretions worldwide, the o13C values of the carbonate Huron Member of the Ohio Shale are distin­ carbonates are strikingly different from those of normal guished by their large size (to 3-m diam.), their high degree marine limestones but are similar to those of organic carbon of sphericity, and their common association with the remains and diagenetic carbonates. We demonstrate that the of arthrodire fish. Field relationships and the high ratio of observed o13C values are similar to those of fish-bearing authigenic to detrital components in the concretions indicate concretions from several other marine sequences, and we that they underwent rapid, early diagenetic growth as soft, propose, along with Berner (1968), that such concretions low-density bodies that cemented the void space of extre­ may have originated as bodies of adipocere (low-density mely porous (81 < t < 94 percent) sediment near the organic soap) that formed rapidly during decay of proteinac­ sediment-water interface. This early growth phase (stage 1) eous matter in the sediment. was probably associated with precipitation of small amounts of barite and whewellite and was followed by a protracted interval that featured (stage 2) formation of the pyrite rims INTRODUCTION and of small pyrite concretions, concurrent with compaction of the shale and with replacement of the concretions by The Upper Devonian Ohio Shale crops out along a calcite, followed by replacement of the calcite by Ca- and north-south band through central Ohio (fig. 1). In the Fe-rich dolomite (except within the central zones of the lower part (Huron Member) and upper part (Cleveland largest concretions); (stage 3) formation of joints in the shale, Member) of this black shale, there are several horizons followed by intrusion of clastic dikes, severe deformation of that contain carbonate and pyrite concretions, as well as concretions incorporated in the dikes, and continued com­ a few cone-in-cone layers. These large, unusual, and paction of the shale; and (stage 4) complex recrystallization and replacement of the concretions, represented by partial commonly fossiliferous concretions (fig. 2) were dissolution and recrystallization of the calcite centers, growth described by the earliest geologic investigators in Ohio, of quartz, dolomite, and calcite in vugs and veins, and and several proposals were made for the conditions ana approximately concurrent growth of cone-in-cone layers in causes of their formation. Much disagreement arose over the shale. Oxygen isotope data (-5.5<o180< -2.5) of the the temporal relations of the concretions relative to the dolomitic matrix of the concretions are consistent with the degree of compaction of the surrounding shale (New­ early rapid growth and replacement stages (1 and 2) occur­ berry, 1873; Daly, 1900; Westgate, 1926), although sub­ ring at low but progressively increasing temperatures in sequently Clifton (1957) presented convincing arguments 18 marine pore fluid. o 0 values of about -10 for recrystallized for their penecontemporaneous growth (see below). matrix calcite, most vug calcites, and a cone-in-cone layer Other investigators focused on the chemistry and mine­ suggest that stage 4 growth occurred at moderate tempera­ ralogy of the black shale and made conflicting sug­ tures (perhaps 75 °C) in the presence of marine pore fluid or, perhaps more likely, formation water that penetrated the gestions for the source of the organic matter, the post­ shale at a later time. A noteworthy paradox is that, in the early depositional conditions that led to its preservation, and portions of the proposed sequence, the highly porous, the environment of deposition (see summary by Hoover, low-density (p < 1.5) sediment could seemingly not have 1960). Studies of concretions from other localities and application of modern analytical techniques to concre­ 1 U.S.